DE3102690C2 - CdO- and ThO? 2? -Free optical glass with a refractive index of 1.75-1.82 and an Abbe value of 37-48 in the system B? 2? O? 3? - La 2 O 3 - Y? 2? O? 3? - Nb 2 O 5 - ZnO - ZrO 2 - Google Patents

CdO- and ThO? 2? -Free optical glass with a refractive index of 1.75-1.82 and an Abbe value of 37-48 in the system B? 2? O? 3? - La 2 O 3 - Y? 2? O? 3? - Nb 2 O 5 - ZnO - ZrO 2

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Publication number
DE3102690C2
DE3102690C2 DE19813102690 DE3102690A DE3102690C2 DE 3102690 C2 DE3102690 C2 DE 3102690C2 DE 19813102690 DE19813102690 DE 19813102690 DE 3102690 A DE3102690 A DE 3102690A DE 3102690 C2 DE3102690 C2 DE 3102690C2
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Germany
Prior art keywords
weight
zro
zno
refractive index
cdo
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DE19813102690
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German (de)
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DE3102690A1 (en
Inventor
Volkmar 6500 Mainz Geiler
Karl Dr. 6204 Taunusstein Mennemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
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Schott Glaswerke 6500 Mainz
Schott Glaswerke AG
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Priority to DE19813102690 priority Critical patent/DE3102690C2/en
Publication of DE3102690A1 publication Critical patent/DE3102690A1/en
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Publication of DE3102690C2 publication Critical patent/DE3102690C2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Das neue optische Glas hat die optische Lage nd = 1,75-1,82 und vd = 37-48 und besteht aus (in Gew.%): 26-34 B ↓2O ↓3, 30-43 La ↓2O ↓3, 2-12 Y ↓2O ↓3, 5,2-11 Nb ↓2O ↓5 und 2-18 ZnO, wobei La ↓2O ↓3 + Y ↓2O ↓3 38-46 Gew.% betragen müssen. Seine Vorteile liegen darin, daß es kein Cadmiumoxid oder Thoriumoxid enthält und eine ausgezeichnete Entglasungsstabilität aufweist.The new optical glass has the optical position nd = 1.75-1.82 and vd = 37-48 and consists of (in% by weight): 26-34 B ↓ 2O ↓ 3, 30-43 La ↓ 2O ↓ 3 , 2-12 Y ↓ 2O ↓ 3, 5.2-11 Nb ↓ 2O ↓ 5 and 2-18 ZnO, where La ↓ 2O ↓ 3 + Y ↓ 2O ↓ 3 must be 38-46% by weight. Its advantages are that it does not contain cadmium oxide or thorium oxide and has excellent devitrification stability.

Description

2. Glas nach Anspruch 1, dadurch gekennzeichnet, daß es zusätzlich2. Glass according to claim 1, characterized in that it is additionally

O - 7,0 Gew.-% SiO2 undO - 7.0 wt% SiO 2 and

0 - 7,0 Gew.~% Al2O3 enthält,Contains 0 - 7.0 wt.% Al 2 O 3,

wobei B2O3 + SiO2 + Al2O3 = 28-38 Gew.-%where B 2 O 3 + SiO 2 + Al 2 O 3 = 28-38% by weight

3. Glas nach Ansprach 1 oder 2, dadurch gekennzeichnet, daß es zusätzlich :3. Glass according to spoke 1 or 2, characterized in that that it also:

O - 8,0 Gew.-% PbO enthält.Contains O - 8.0 wt% PbO.

4. Glas nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es zusätzlich4. Glass according to one of claims 1 to 3, characterized in that it is additionally

O - 8,0 Gew.-%TiO2 enthält.Contains O - 8.0 wt% TiO 2.

5. Glas nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es zusätzlich5. Glass according to one of claims 1 to 4, characterized in that it is additionally

O - 7,0 Gew.-% MgO
O - 8,0 Gew.-% CaO
O- 11,0 Gew.-% BaO
0-10,0 Gew.-% SrO enthält,O - 7.0 wt% MgO
O - 8.0 wt% CaO
O- 11.0 wt% BaO
Contains 0-10.0% by weight of SrO,

wobei MgO + CaO + SrO + BaO ** 16 Gew.-%.where MgO + CaO + SrO + BaO ** 16% by weight.

6. Glas nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es zusätzlich6. Glass according to one of claims 1 to 5, characterized in that it is additionally

0-5 Gew.-% WO3 enthält.Contains 0-5% by weight of WO 3.

7. Glas nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es zusätzlich7. Glass according to one of claims 1 to 6, characterized in that it is additionally

0-8 Gew.-% Gd2O3 enthält, wobei La2O3 + Y2O3 + Gd2O3 = 38-46 Gew.-°/aContains 0-8% by weight of Gd 2 O 3 , where La 2 O 3 + Y 2 O 3 + Gd 2 O 3 = 38-46% by weight / a

8. Glas nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es zusätzlich8. Glass according to one of claims 1 to 7, characterized in that it is additionally

0-4 Gew.-% Ta2O5 enthält.Contains 0-4 wt% Ta 2 O 5.

9. Glas nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es zusätzlich9. Glass according to one of claims 1 to 8, characterized in that it is additionally

ü - 2 uew.-u/o Li2O
0-2 Gew.-% Na2O
0-2 Gew.-% K2Oü - 2 uew.- u / o Li 2 O
0-2 wt% Na 2 O
0-2 wt% K 2 O

6060

enthält,contains,

wobei Li2O + Na2O H- K2O < 2 Gew.-%where Li 2 O + Na 2 O H- K 2 O <2 wt .-%

3030th

3535

4040

45 den giftigen Oxiden des Cadmium und Thorium kostengünstig herzustellen, wobei auf teures Ta2O5 verzichtet werden kann und dennoch eine ausgezeichnete Entglasungsstabilität erreicht wird. 45 to produce the toxic oxides of cadmium and thorium inexpensively, whereby expensive Ta 2 O 5 can be dispensed with and an excellent devitrification stability is nevertheless achieved.

In der GB-PS 9 53 480 sind Glasrezepturen im Glassystem B2O3 - La2O3 - Y2O3 beschrieben, die es jedoch nur erlauben, Gläser mit einem Brechungsindex bis izrf= 1,775 herzustellen, selbst bei Zusatz von Ta2O5, ZrO2, CdO, Nb2O5.In GB-PS 9 53 480 glass formulations in the glass system B 2 O 3 - La 2 O 3 - Y 2 O 3 are described which, however, only allow glasses with a refractive index up to izrf = 1.775 to be produced, even with the addition of Ta 2 O 5 , ZrO 2 , CdO, Nb 2 O 5 .

Gläser ähnlicher optischer Lage wie die der vorliegenden Erfindung werden z. B. beschrieben in der DE-AS 14 21 892, jedoch enthalten diese Gläser teures Ta2O5 und darüber hinaus zusätzlich giftiges CdO.Glasses of similar optical position as those of the present invention are z. B. described in DE-AS 14 21 892, but these glasses contain expensive Ta 2 O 5 and, moreover, additionally toxic CdO.

In der DE-OS 22 59 122 werden optische Gläser im System B2O3 - La2O3 - Gd2O3 - Ta2O5 mit ähnlich optischer Lage beschrieben, die jedoch wegen ihres relativ hohen Tantaloxidgehalts sehr teuer sind und daher für die Massenproduktion ausscheiden.In DE-OS 22 59 122 optical glasses in the system B 2 O 3 - La 2 O 3 - Gd 2 O 3 - Ta 2 O 5 are described with a similar optical position, which, however, are very expensive because of their relatively high tantalum oxide content and therefore retire for mass production.

Ähnliches trifft für die Gläser gemäL der JP-OS 74 214OS zu, die außerdem nicht die Forderung nach guter Entglasungsstabilität erfüllen.The same applies to the glasses according to the JP-OS 74 214OS too, which also does not meet the requirement meet good devitrification stability.

Von den Gläsern nach JP-OS 77 85 210 unterscheidet sich der Anmeldungsgegenstand durch einen höheren Nb2O5-GehaIt, der wesentlich zur Kristallisationsstabilität beiträgtThe subject of the application differs from the glasses according to JP-OS 77 85 210 by a higher Nb 2 O 5 content, which contributes significantly to the crystallization stability

Weiterhin sind aus der FR-PS 23 19 591 Gläser mit ähnlicher optischer Lage wie beim Anmeldungsgegenstand bekanntgeworden; bei diesen bekannten Gläsern ist jedoch offensichtlich zur Vermeidung einer Entglasung, Fluor ein essentieller Bestandteil, der erfindungsgemäß vermieden werden soll.Furthermore, from FR-PS 23 19 591 glasses with a similar optical position as in the subject of the application known; with these known glasses, however, it is obvious to avoid devitrification, Fluorine is an essential component that should be avoided according to the invention.

Schließlich beschreibt auch die DE-AS 2652 747 Gläser in dem vorliegenden Glassystem und mit ähnlicher optischer Lage wie beim Anmeldungsgegenstand, bei denen die Gefahr einer Entglasung in fünf unterschiedlichen Zusammensetzungsbereichen durch sorgfältige Abstimmung der Komponenten TiO2, Y2O3, Ta2O5 und GeO2 zu vermeiden versucht wird.Finally, DE-AS 2652 747 also describes glasses in the present glass system and with a similar optical position as in the subject of the application, in which the risk of devitrification in five different composition ranges due to careful coordination of the components TiO 2 , Y 2 O 3 , Ta 2 O 5 and GeO 2 is attempted to be avoided.

Im Gegensatz zu diesen bekannten Gläsern lassen sich gemäß der Erfindung Gläser hoher Entglasungsstabilität der optischen Lage nd = 1,75 - 1,82 und vd= 37 - 48 im Glassystem B2O3 - La2O3 - Y2O3 Nb2O5 - ZrO2 herstellen, die durch ZnO gegen Entglasung geschützt sind.In contrast to these known glasses, according to the invention glasses with high devitrification stability of the optical layer nd = 1.75-1.82 and vd = 37-48 in the glass system B 2 O 3 - La 2 O 3 - Y 2 O 3 Nb 2 Produce O 5 - ZrO 2 , which are protected against devitrification by ZnO.

Der Anmeldungsgegenstand ist gekennzeichnet durch folgenden Zusanunensetzungsbereich:The subject of the registration is characterized by the following composition area:

5050

6565

Ziel der vorliegenden Erfindung ist esr Gläser der . optischen Lage nd= 1,75 -1,82 und W= 37 - 48 frei vonThe aim of the present invention is to r glasses. optical position nd = 1.75-1.82 and W = 37-48 free of

B2O3 B 2 O 3 3030th - 34 Gew.-%- 34% by weight 7 Gew.-%7% by weight La2O3 La 2 O 3 3535 - 39 Gew.-%- 39% by weight 7 Gew.-%7% by weight Y2O3 Y 2 O 3 22 - 8 Gew.-%- 8% by weight 2 Gew.-o/o2 wt. O / o Nb2O5 Nb 2 O 5 66th - 9 Gew.-%- 9% by weight 2 Gew.-%2% by weight ZnOZnO 66th - 9 Gew.-"/o- 9 wt .- "/ o 2 Gew.-%2% by weight ZrO2 ZrO 2 44th - 8 Gew.-0/α- 8% by weight / α 7 Gew.-% 7 % by weight llweisell wise können zugesetzt werden:can be added: 8 Gew.-%8% by weight SiO2 SiO 2 0-0- 11 Gew.-o/o11 wt. O / o Al2O3 Al 2 O 3 0-0- 10 Gew.-%10% by weight Li2OLi 2 O 0-0- 8 Gew.-%8% by weight Na2 Well 2 0-0- 8 Gew.-%8% by weight K2OK 2 O 0-0- 8 Gew.-%8% by weight MgOMgO 0-0- CaOCaO 0-0- BaOBaO 0-0- SrOSrO 0-0- PbOPbO 0-0- TiO2 TiO 2 0-0- Gd2O3 Gd 2 O 3 0-0-

WO3
Ta2O5 WHERE 3
Ta 2 O 5

0-0-0-0-

5 Gew.-%
4 Gew.-%.5% by weight
4% by weight.

Als bedeutsam erweist sich der Anteil der SE-Oxide (La2Oj + Y2Oj + Gd2O3), der zwischen 38 und 46 Gew.-%liegen soll, sowie die gleichzeitige Anwesenheit von La2O3 und Y2O3; hierbei muß der Anteil des Y2O3 > 2 Gew.-% sein, um einen genügenden Stabilisierungseffekt zu erzielen, andererseits sollte er 8 Gew.-°/o nicht überschreiten, da sich dann der günstige stabilisierende Effekt in sein Gegenteil verkehrt. The proportion of rare earth oxides (La 2 Oj + Y 2 Oj + Gd 2 O 3 ), which should be between 38 and 46% by weight, and the simultaneous presence of La 2 O 3 and Y 2 O have proven to be significant 3 ; the proportion of Y 2 O 3 must be > 2% by weight in order to achieve a sufficient stabilizing effect; on the other hand, it should not exceed 8% by weight, since the beneficial stabilizing effect is then reversed.

Als weitere essentielle Komponente unterstützt das Nb2Os das B2O3 als Glasbildner und sorgt darüber hinaus für einen genügend hohen Brechwert.As a further essential component, the Nb 2 Os supports the B 2 O 3 as a glass former and also ensures a sufficiently high refractive index.

Dieser Grundsynthese können je nach Bedarf SiO2 und/oder AI2O3 in Anteilen < 7 Gew.-% zugesetzt werden; auch sind Alkalioxide S 2 Gew.-°/o erlaubt, ferner Erdalkalioxide « 16 Gew.-%Depending on requirements, SiO 2 and / or Al 2 O 3 can be added to this basic synthesis in proportions of <7% by weight; Alkali oxides S 2% by weight are also allowed, furthermore alkaline earth oxides <16% by weight

ZrO2 erweist sich bis zu 8 Gew.-% als nützlich; zum einen wirkt es brechwerterhöhend, zum anderen verbessert es die chemische Resistenz. PbO, TiO2, WO3 dienen zur Brechwertkorrektur; auf Ta2O5 kann ganz verzichtet werden, sein Zusatz ist jedoch erlaubt.ZrO 2 is found to be useful up to 8% by weight; On the one hand, it increases the refractive index; on the other hand, it improves chemical resistance. PbO, TiO 2 , WO 3 are used to correct the refractive index; Ta 2 O 5 can be dispensed with entirely, but its addition is permitted.

Gläser entsprechend dieser Erfindung werden folgendermaßen hergestellt: als Rohstoff werden'die entsprechenden Oxide, Nitrate, Carbonate benutzt; diese werden gemäß dem Rezept abgewogen, und ein kleiner Anteil Läutermittel, wie z. B. As2O3 wird zugesetzt. Dieses Glasgemenge wird gut gemischt in einen auf 1200° C - 1400° C erhitzten Platintiegel gegeben und bei dieser Temperatur geschmolzen. Nach dem Läutern wird das Glas mittels Rührer gut homogenisiert, bis zur Gußtemperatur von ca. lOöß — 1100° C abgerührt und in i ;ne Eisenform gegossen.Glasses according to this invention are produced as follows: the corresponding oxides, nitrates and carbonates are used as raw materials; these are weighed according to the recipe, and a small amount of refining agents, such as. B. As 2 O 3 is added. This glass batch is mixed well and placed in a platinum crucible heated to 1200 ° C - 1400 ° C and melted at this temperature. After fining, the glass is homogenized by stirring, until the casting temperature of about lOöß - 1100 ° C and in abgerührt i; cast an iron mold.

Die Tabelle gibt Zusammensetzungen von Gläsern gemäß der Erfindung und ihre optischen Daten wieder.The table shows compositions of glasses according to the invention and their optical data.

TabelleTabel

B2O3 B 2 O 3 32,6032.60 31,0031.00 30,330.3 33,8033.80 31,8031.80 SiO2 SiO 2 —- —- 4,004.00 —- —- Al2O3 Al 2 O 3 —- —- 1,501.50 —- —- CaOCaO 0,850.85 —- —- —- SrOSrO —- 0,900.90 —- —- —- BaOBaO 3,503.50 —- —- -- -- ZnOZnO 7,107.10 8,508.50 9,09.0 7,507.50 8,008.00 PbOPbO 1,101.10 1,001.00 -- —- -- TiO2 TiO 2 0,430.43 2,502.50 7,007.00 —- 2,202.20 ZrO2 ZrO 2 6,706.70 7,007.00 4,004.00 7,007.00 6,806.80 Nb2O5 Nb 2 O 5 7,357.35 7,307.30 6,006.00 9,009.00 7,507.50 La2O3 La 2 O 3 38,4038.40 37,8037.80 35,9035.90 35,0035.00 37,8037.80 Y2O3 Y 2 O 3 2,002.00 4,004.00 2,302.30 7,70 .7.70. 3,903.90 Li2O 0,50Li 2 O 0.50 Na2O 0,50Na 2 O 0.50 K2O 1,00K 2 O 1.00 ndnd 1,78451.7845 1,80801.8080 1,79401.7940 1,78501.7850 1,79601.7960 vdvd 43,943.9 40,740.7 37,837.8 43,043.0 41,541.5

Claims (1)

3ί 023ί 02 Patentansprüche:Patent claims: L CdO- und ThOrfreies optisches Glas mit den optischen Werten nd= 1,75 - 1,82 und vd= 37 - 48, im System B2O3 - La2O3 - Y2O3 - Nb2O5 - ZnO ZrO2, gekennzeichnet durch folgende Zusammensetzung (in Gew.-%)L CdO- and Thor-free optical glass with the optical values nd = 1.75-1.82 and vd = 37-48 , in the system B 2 O 3 - La 2 O 3 - Y 2 O 3 - Nb 2 O 5 - ZnO ZrO 2 , characterized by the following composition (in% by weight) B2O3 B 2 O 3 30,030.0 -34,0-34.0 La2O3 La 2 O 3 35,035.0 -39,0-39.0 Y2O3 Y 2 O 3 2,02.0 - 8,0- 8.0 Nb2O5 Nb 2 O 5 6,06.0 - 9,0- 9.0 ZnOZnO 6,06.0 - 9,0- 9.0 ZrO2 ZrO 2 4,04.0 - 8,0- 8.0 La2O3 + Y2O3 La 2 O 3 + Y 2 O 3 3838 -46-46
1010
DE19813102690 1981-01-28 1981-01-28 CdO- and ThO? 2? -Free optical glass with a refractive index of 1.75-1.82 and an Abbe value of 37-48 in the system B? 2? O? 3? - La 2 O 3 - Y? 2? O? 3? - Nb 2 O 5 - ZnO - ZrO 2 Expired DE3102690C2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19813102690 DE3102690C2 (en) 1981-01-28 1981-01-28 CdO- and ThO? 2? -Free optical glass with a refractive index of 1.75-1.82 and an Abbe value of 37-48 in the system B? 2? O? 3? - La 2 O 3 - Y? 2? O? 3? - Nb 2 O 5 - ZnO - ZrO 2

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813102690 DE3102690C2 (en) 1981-01-28 1981-01-28 CdO- and ThO? 2? -Free optical glass with a refractive index of 1.75-1.82 and an Abbe value of 37-48 in the system B? 2? O? 3? - La 2 O 3 - Y? 2? O? 3? - Nb 2 O 5 - ZnO - ZrO 2

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TW593195B (en) * 2001-02-05 2004-06-21 Koninkl Philips Electronics Nv Multicomponent glass, glass fiber, twister and taper
JP4093524B2 (en) 2001-02-20 2008-06-04 Ｈｏｙａ株式会社 Optical glass, press-molding preform and optical parts
JP4017832B2 (en) * 2001-03-27 2007-12-05 Ｈｏｙａ株式会社 Optical glass and optical components
DE10122263C2 (en) * 2001-05-08 2003-04-03 Schott Glas Optical glasses and their use
DE102004009930B4 (en) * 2004-02-26 2008-07-24 Schott Ag Lead- and arsenic-free optical lanthanum flint glasses and their use
JP4350016B2 (en) * 2004-09-29 2009-10-21 Ｈｏｙａ株式会社 Optical glass, precision press-molding preform and manufacturing method thereof, and optical element and manufacturing method thereof
DE102005020423B4 (en) 2005-04-29 2009-04-02 Schott Ag Lead- and arsenic-free optical lanthanum borate glass and its use
CN107879620B (en) * 2016-09-29 2020-12-29 成都光明光电股份有限公司 Optical glass, glass preform and optical element
CN109734304B (en) * 2019-03-28 2021-12-07 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN111977970B (en) * 2020-09-07 2022-04-15 成都光明光电股份有限公司 Optical glass and optical element

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JPS5215510A (en) * 1975-07-28 1977-02-05 Nippon Chemical Ind Optical glass
JPS5263211A (en) * 1975-11-20 1977-05-25 Nippon Chemical Ind Optical glass

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